Internal donor for olefin polymerization catalysts

ABSTRACT

Disclosed are solid titanium catalyst components, catalyst systems containing solid titanium catalyst components, and methods of making solid titanium catalyst components. The solid titanium catalyst components contain an internal electron donor compound containing at least one ether group and at least one ketone group. The catalyst system can contain a solid titanium catalyst component, an organoaluminum compound, and an organosilicon compound. Also disclosed are methods of polymerizing or copolymerizing an alpha-olefin. The methods involve contacting an olefin with a catalyst system containing the solid titanium catalyst component.

TECHNICAL FIELD

The subject innovation generally relates to solid titanium catalystcomponents, catalyst systems containing solid titanium catalystcomponents, methods of making solid titanium catalyst components, andmethods of polymerizing or copolymerizing an alpha-olefin using acatalyst system containing a solid titanium catalyst component.

BACKGROUND

Polyolefins are a class of polymers derived from simple olefins. Knownmethods of making polyolefins involve the use of Ziegler-Nattapolymerization catalysts. These catalysts polymerize vinyl monomersusing a transition metal halide to provide a stereoregulated polymer.

Numerous Ziegler-Natta polymerization catalysts exist. The catalystshave different characteristics and/or lead to the production ofpolyolefins having diverse properties. For example, certain catalystshave high activity while other catalysts have low activity, andsimilarly certain catalysts have a long life while other catalysts havea short life. Moreover, polyolefins made with the use of Ziegler-Nattapolymerization catalysts vary in stereoregularity, molecular weightdistribution, impact strength, melt-flowability, rigidity, heatsealability, isotacticity, and the like.

Useful Ziegler-Natta polymerization catalysts made through aprecipitation method are made using an organic magnesium compoundstarting material. The organic magnesium compound leads to the formationof a desirable spherical catalyst particle. Replacing the organicmagnesium compound starting material with a markedly less expensivemagnesium halide results in a catalyst particle with a morphology thatis difficult to control and aspherical or the use of expensive capitalprocesses such as spray congealing (processes where MgCl₂ is mixed withethanol, heated to form a meld, and then sprayed through a nozzle into acold liquid or gas).

SUMMARY

The following presents a simplified summary of the innovation in orderto provide a basic understanding of some aspects of the innovation. Thissummary is not an extensive overview of the innovation. It is intendedto neither identify key or critical elements of the innovation nordelineate the scope of the innovation. Rather, the sole purpose of thissummary is to present some concepts of the innovation in a simplifiedform as a prelude to the more detailed description that is presentedhereinafter.

The subject innovation provides solid titanium catalyst components foruse in olefinic polymerization, olefin polymerization catalyst systems,methods of making solid titanium catalyst components, and methods ofpolymerizing and copolymerizing olefins involving the use of a solidtitanium catalyst component. The solid titanium catalyst componentscontain a titanium compound, a magnesium compound, and an internalelectron donor compound containing at least one ether group and at leastone ketone group. The catalyst system can contain a solid titaniumcatalyst component, an organoaluminum compound, and an organosiliconcompound. The titanium catalyst component can be made by contacting amagnesium compound and a titanium compound with an internal electrondonor compound containing at least one ether group and at least oneketone group.

The subject innovation also provides methods of polymerizing orcopolymerizing an olefin. The methods involve contacting an olefin witha catalyst system containing a solid titanium catalyst component, anorganoaluminum compound; and an organosilicon compound. The solidtitanium catalyst component contains an internal electron donor compoundcontaining at least one ether group and at least one ketone group.

To the accomplishment of the foregoing and related ends, the innovationinvolves the features hereinafter fully described and particularlypointed out in the claims. The following description and the annexeddrawings set forth in detail certain illustrative aspects andimplementations of the innovation. These are indicative, however, of buta few of the various ways in which the principles of the innovation maybe employed. Other objects, advantages and novel features of theinnovation will become apparent from the following detailed descriptionof the innovation when considered in conjunction with the drawings.

BRIEF SUMMARY OF THE DRAWINGS

FIG. 1 is a high level schematic diagram of an olefin polymerizationsystem in accordance with one aspect of the subject innovation.

FIG. 2 is a schematic diagram of an olefin polymerization reactor inaccordance with one aspect of the subject innovation.

FIG. 3 is a high level schematic diagram of a system for making impactcopolymer in accordance with one aspect of the subject innovation.

DETAILED DESCRIPTION

The subject innovation relates to solid titanium catalyst components(e.g., catalyst support) for use in olefinic polymerization, olefinpolymerization catalyst systems, methods of making solid titaniumcatalyst components, and methods of polymerizing and copolymerizingolefins involving the use of a solid titanium catalyst component.

An aspect of the innovation is solid titanium catalyst componentscontaining a titanium compound, a magnesium compound, and an internalelectron donor compound. The internal electron donor compound containsat least one ether group and at least one ketone group. Use of theinternal electron donor compound containing at least one ether group andat least one ketone group can contribute to good performancecharacteristics of resultant catalysts, such as high catalyst activity,high hydrogen response, and the ability to produce polyolefin withdesired/controllable xylene solubles values, desired/controllable meltflow indexes, and the like.

The solid titanium catalyst component of the subject innovation is ahighly active catalyst component containing a titanium compound; amagnesium compound; and an internal electron donor compound containingat least one ether group and at least one ketone group. The titaniumcompounds used in the preparation of the solid titanium catalystcomponent include, for example, a tetravalent titanium compoundrepresented by Formula (I)

Ti(OR)_(g)X_(4-g)  (I)

wherein each R independently represents a hydrocarbon group, preferablyan alkyl group having 1 to about 4 carbon atoms, X represents a halogenatom, and 0≦g≦4. Specific examples of the titanium compound includetitanium tetrahalides such as TiCl₄, TiBr₄ and Til₄; alkoxytitaniumtrihalides such as Ti(OCH₃)Cl₃, Ti(OC₂H₅)Cl₃, Ti(O-n-C₄H₉)Cl₃,Ti(OC₂H₅)Br₃ and Ti(O-1-C₄H₉)Br₃; dialkoxytitanium dihalides such asTi(OCH₃)₂ Cl₂, Ti(OC₂H₅)₂Cl₂, Ti(O-n-C₄H₉)₂Cl₂ and Ti(OC₂H₅)₂Br₂;trialkoxytitanium monohalides such as Ti(OCH₃)₃Cl, Ti(OC₂H₅)₃Cl,Ti(O-n-C₄H₉)₃Cl and Ti(OC₂H₅)₃Br; and tetraalkoxytitaniums such asTi(OCH₃)₄, Ti(OC₂H₅)₄ and Ti(O-n-C₄H₉)₄.

Among these, the halogen containing titanium compounds, especiallytitanium tetrahalides, are preferred in some instances. These titaniumcompounds may be used individually or in solutions of hydrocarboncompounds or halogenated hydrocarbons.

The magnesium compounds used in the preparation of the solid titaniumcatalyst component include, for example, a magnesium compound having noreducibility. In one embodiment, the magnesium compound having noreducibility is a halogen containing magnesium compound. Specificexamples of the magnesium compound having no reducibility includemagnesium halides such as magnesium chloride, magnesium bromide,magnesium iodide and magnesium fluoride; alkoxy magnesium halides suchas methoxy magnesium chloride, ethoxy magnesium chloride, isopropoxymagnesium chloride, butoxy magnesium chloride and octoxy magnesiumchloride; aryloxy magnesium halides such as phenoxy magnesium chlorideand methylphenoxy magnesium chloride; alkoxy magnesiums such as ethoxymagnesium, isopropoxy magnesium, butoxy magnesium, n-octoxy magnesiumand 2-ethylhexoxy magnesium; aryloxy magnesiums such as phenoxymagnesium and dimethylphenoxy magnesium; and carboxylic acid salts ofmagnesium such as magnesium laurate and magnesium stearate. Thesemagnesium compounds may be in the liquid or solid state.

In one aspect, halogen containing magnesium compounds, such as magnesiumchloride, alkoxy magnesium chlorides and aryloxy magnesium chlorides,are employed.

When preparing the solid titanium catalyst component, an internalelectron donor can be used/added. The solid titanium catalyst componentcan be made by contacting a magnesium compound and a titanium compoundwith an internal electron donor. In one embodiment, the solid titaniumcatalyst component is made by contacting a magnesium compound and atitanium compound in the presence of an internal electron donor. Inanother embodiment, the solid titanium catalyst component is made byforming a magnesium based catalyst support optionally with the titaniumcompound and optionally with the internal electron donor, and contactingthe magnesium based catalyst support with the titanium compound and theinternal electron donor.

The internal electron donor contains at least one ether group and atleast one ketone group. That is, the internal electron donor compoundcontains in its structure at least one ether group and at least oneketone group.

Examples of internal electron donors containing at least one ether groupand at least one ketone group include compounds of the following Formula(II).

wherein R¹, R², R³, and R⁴ are identical or different, and eachrepresents a substituted or unsubstituted hydrocarbon group. In oneembodiment, the substituted or unsubstituted hydrocarbon group includesfrom 1 to about 30 carbon atoms. In another embodiment, R¹, R², R³, andR⁴ are identical or different, and each represents a linear or branchedalkyl group containing from 1 to about 18 carbon atoms, a cycloaliphaticgroup containing from about 3 to about 18 carbon atoms, an aryl groupcontaining from about 6 to about 18 carbon atoms, an alkylaryl groupcontaining from about 7 to about 18 carbon atoms, and an arylalkyl groupcontaining from about 7 to about 18 carbon atoms. In yet anotherembodiment, R¹, C¹ and R² are a part of a substituted or unsubstitutedcyclic or polycyclic structure containing from about 5 to about 14carbon atoms. In still yet another embodiment, the cyclic or polycyclicstructure has one or more substitutes selected from the group consistingof a linear or branched alkyl group containing from 1 to about 18 carbonatoms, a cycloaliphatic group containing from about 3 to about 18 carbonatoms, an aryl group containing from about 6 to about 18 carbon atoms,an alkylaryl group containing from about 7 to about 18 carbon atoms, andan arylalkyl group containing from about 7 to about 18 carbon atoms.

Specific examples of internal electron donors containing at least oneether group and at least one ketone group include9-(alkylcarbonyl)-9′-alkoxymethylfluorene including9-(methylcarbonyl)-9′-methoxymethylfluorene,9-(methylcarbonyl)-9′-ethoxymethylfluorene,9-(methylcarbonyl)-9′-propoxymethylfluorene,9-(methylcarbonyl)-9′-butoxymethylfluorene,9-(methylcarbonyl)-9′-pentoxymethylfluorene,9-(ethylcarbonyl)-9′-methoxymethylfluorene,9-(ethylcarbonyl)-9′-ethoxymethylfluorene,9-(ethylcarbonyl)-9′-propoxymethylfluorene,9-(ethylcarbonyl)-9′-butoxymethylfluorene,9-(ethylcarbonyl)-9′-pentoxymethylfluorene,9-(propylcarbonyl)-9′-methoxymethylfluorene,9-(propylcarbonyl)-9′-ethoxymethylfluorene,9-(propylcarbonyl)-9′-propoxymethylfluorene,9-(propylcarbonyl)-9′-butoxymethylfluorene,9-(propylcarbonyl)-9′-pentoxymethylfluorene,9-(butylcarbonyl)-9′-methoxymethylfluorene,9-(butylcarbonyl)-9′-ethoxymethylfluorene,9-(butylcarbonyl)-9′-propoxymethylfluorene,9-(butylcarbonyl)-9′-butoxymethylfluorene,9-(butylcarbonyl)-9′-pentoxymethylfluorene,9-(pentylcarbonyl)-9′-methoxymethylfluorene,9-(pentylcarbonyl)-9′-ethoxymethylfluorene,9-(pentylcarbonyl)-9′-propoxymethylfluorene,9-(pentylcarbonyl)-9′-butoxymethylfluorene,9-(pentylcarbonyl)-9′-pentoxymethylfluorene,9-(hexylcarbonyl)-9′-methoxymethylfluorene,9-(hexylcarbonyl)-9′-ethoxymethylfluorene,9-(hexylcarbonyl)-9′-propoxymethylfluorene,9-(hexylcarbonyl)-9′-butoxymethylfluorene,9-(hexylcarbonyl)-9′-pentoxymethylfluorene,9-(octylcarbonyl)-9′-methoxymethylfluorene,9-(octylcarbonyl)-9′-ethoxymethylfluorene,9-(octylcarbonyl)-9′-propoxymethylfluorene,9-(octylcarbonyl)-9′-butoxymethylfluorene,9-(octylcarbonyl)-9′-pentoxymethylfluorene;9-(i-octylcarbonyl)-9′-methoxymethylfluorene,9-(i-octylcarbonyl)-9′-ethoxymethylfluorene,9-(i-octylcarbonyl)-9′-propoxymethylfluorene,9-(i-octylcarbonyl)-9′-butoxymethylfluorene,9-(i-octylcarbonyl)-9′-pentoxymethylfluorene;9-(i-nonylcarbonyl)-9′-methoxymethylfluorene,9-(i-nonylcarbonyl)-9′-ethoxymethylfluorene,9-(i-nonylcarbonyl)-9′-propoxymethylfluorene,9-(i-nonylcarbonyl)-9′-butoxymethylfluorene,9-(i-nonylcarbonyl)-9′-pentoxymethylfluorene;9-(2-ethyl-hexylcarbonyl)-9′-methoxymethylfluorene,9-(2ethyl-hexylcarbonyl)-9′-ethoxymethylfluorene,9-(2-ethyl-hexylcarbonyl)-9′-propoxymethylfluorene,9-(2-ethyl-hexylcarbonyl)-9′-butoxymethylfluorene,9-(2-ethyl-hexylcarbonyl)-9′-pentoxymethylfluorene,9-(phenylketone)-9′-methoxymethylfluorene,9-(phenylketone-9′-ethoxymethylfluorene,9-(phenylketone)-9′-propoxymethylfluorene,9-(phenylketone)-9′-butoxymethylfluorene,9-(phenylketone)-9′-pentoxymethylfluorene,9-(4-methylphenylketone)-9′-methoxymethylfluorene,9-(3-methylphenylketone)-9′-methoxymethylfluorene,9-(2-methylphenylketone)-9′-methoxymethylfluorene.

Additional examples include:1-(ethylcarbonyl)-1′-methoxymethylcyclopentane,1-(propylcarbonyl)-1′-methoxymethylcyclopentane,1-(i-propylcarbonyl)-1′-methoxymethylcyclopentane,1-(butylcarbonyl)-1′-methoxymethylcyclopentane,1-(i-butylcarbonyl)-1′-methoxymethylcyclopentane.1-(pentylcarbonyl)-1′-methoxymethylcyclopentane,1-(i-pentylcarbonyl)-1′-methoxymethylcyclopentane,1-(neopentylcarbonyl)-1′-methoxymethylcyclopentane,1-(hexhylcarbonyl)-1′-methoxymethylcyclopentane,1-(2-ethylhexylcarbonyl)-1′-methoxymethylcyclopentane,1-(octylcarbonyl)-1′-methoxymethylcyclopentane,1-(i-octylcarbonyl)-1′-methoxymethylcyclopentane,1-(i-nonylcarbonyl)-1′-methoxymethylcyclopentane.1-(ethylcarbonyl)-1′-methoxymethyl-2-methylcyclopentane,1-(propylcarbonyl)-1′-methoxymethyl-2-methylcyclopentane,1-(i-propylcarbonyl)-1′-methoxymethyl-2-methyl-cyclopentane,1-(butylcarbonyl)-1′-methoxymethyl-2-methylcyclopentane,1-(i-butylcarbonyl)-1′-methoxymethyl-2-methylcyclopentane.1-(pentylcarbonyl)-1′-methoxymethyl-2-methylcyclopentane,1-(i-pentylcarbonyl)-1′-methoxymethyl-2-methylcyclopentane,1-(neopentylcarbonyl)-1′-methoxymethyl-2-methylcyclopentane,1-(hexhylcarbonyl)-1′-methoxymethyl-2-methylcyclopentane,1-(2-ethylhexylcarbonyl)-1′-methoxymethyl-2-methyl cyclopentane,1-(octylcarbonyl)-1′-methoxymethyl-2-methyl cyclopentane,1-(i-octylcarbonyl)-1′-methoxymethyl-2-methyl cyclopentane,1-(i-nonylcarbonyl)-1′-methoxymethyl-2-methyl cyclopentane,1-(ethylcarbonyl)-1′-methoxymethyl-2,5-dimethylcyclopentane,1-(propylcarbonyl)-1′-methoxymethyl-2,5-dimethylcyclopentane,1-(i-propylcarbonyl)-1′-methoxymethyl-2,5-dimethyl-cyclopentane,1-(butylcarbonyl)-1′-methoxymethyl-2,5-di-cyclopentane,1-(i-butylcarbonyl)-1′-methoxymethyl-2,5-dimethylcyclopentane.1-(pentylcarbonyl)-1′-methoxymethyl-2,5-dimethylcyclopentane,1-(i-pentylcarbonyl)-1′-methoxymethyl-2,5-dimethylcyclopentane,1-(neopentylcarbonyl)-1′-methoxymethyl-2,5-dimethylcyclopentane,1-(hexhylcarbonyl)-1′-methoxymethyl-2,5-dimethylcyclopentane,1-(2-ethylhexylcarbonyl)-1′-methoxymethyl-2,5-dimethyl cyclopentane,1-(octylcarbonyl)-1′-methoxymethyl-2,5-dimethyl cyclopentane,1-(i-octylcarbonyl)-1′-methoxymethyl-2,5-dimethyl cyclopentane,1-(i-nonylcarbonyl)-1′-methoxymethyl-2,5-dimethyl cyclopentane,1-(ethylcarbonyl)-1′-methoxymethylcyclohexane,1-(propylcarbonyl)-1′-methoxymethylcyclohexane,1-(i-propylcarbonyl)-1′-methoxymethylcyclohexane,1-(butylcarbonyl)-1′-methoxymethylcyclohexyl,1-(i-butylcarbonyl)-1′-methoxymethylcyclohexane,1-(pentylcarbonyl)-1′-methoxymethylcyclohexane,1-(i-pentylcarbonyl)-1′-methoxymethylcyclohexane,1-(neopentylcarbonyl)-1′-methoxymethylcyclohexane.1-(hexhylcarbonyl)-1′-methoxymethylcyclohexane,1-(2-ethylhexylcarbonyl)-1′-methoxymethylcyclohexane,1-(octylcarbonyl)-1′-methoxymethylcyclohexane,1-(i-octylcarbonyl)-1′-methoxymethylcyclohexane,1-(i-nonylcarbonyl)-1′-methoxymethylcyclohexane.1-(ethylcarbonyl)-1′-methoxymethyl-2-methylcyclohexane,1-(propylcarbonyl)-1′-methoxymethyl-2-methylcyclohexane,1-(i-propanecarbonyl)-1′-methoxymethyl-2-methyl-cyclohexane,1-(butylcarbonyl)-1′-methoxymethyl-2-methylcyclohexane,1-(i-butylcarbonyl)-1′-methoxymethyl-2-methylcyclohexane.1-(pentylcarbonyl)-1′-methoxymethyl-2-methylcyclohexane,1-(i-pentylcarbonyl)-1′-methoxymethyl-2-methylcyclohexane,1-(neopentylcarbonyl)-1′-methoxymethyl-2-methylcyclohexane,1-(hexhylcarbonyl)-1′-methoxymethyl-2-methylcyclohexane,1-(2-ethylhexylcarbonyl)-1′-methoxymethyl-2-methyl cyclohexane,1-(octylcarbonyl)-1′-methoxymethyl-2-methyl cyclohexane,1-(i-octylcarbonyl)-1′-methoxymethyl-2-methyl cyclohexane,1-(i-nonylcarbonyl)-1′-methoxymethyl-2-methyl cyclohexane,1-(ethylcarbonyl)-1′-methoxymethyl-2,6-dimethylcyclohexane,1-(propylcarbonyl)-1′-methoxymethyl-2,6-dimethylcyclohexane,1-(i-propylcarbonyl)-1′-methoxymethyl-2,6-dimethyl-cyclohexane,1-(butylcarbonyl)-1′-methoxymethyl-2,6-dimethyl-cyclohexane,1-(i-butylcarbonyl)-1′-methoxymethyl-2,6-dimethylcyclohexane.1-(pentylcarbonyl)-1′-methoxymethyl-2,6-dimethylcyclohexane,1-(i-pentylcarbonyl)-1′-methoxymethyl-2,6-dimethylcyclohexane,1-(neopentylcarbonyl)-1′-methoxymethyl-2,6-dimethylcyclohexane,1-(hexhylcarbonyl)-1′-methoxymethyl-2,6-dimethylcyclohexane,1-(2-ethylhexylcarbonyl)-1′-methoxymethyl-2,6-dimethyl cyclohexane,1-(octylcarbonyl)-1′-methoxymethyl-2,6-dimethyl cyclohexane,1-(i-octylcarbonyl)-1′-methoxymethyl-2,6-dimethyl cyclohexane,1-(i-nonylcarbonyl)-1′-methoxymethyl-2,6-dimethyl cyclohexane,2,5-dimethyl-3-ethylcarbonyl-3′-methoxymethylpentane,2,5-dimethyl-3-propylcarbonyl-3′-methoxymethylpentane,2,5-dimethyl-3-propylcarbonyl-3′-methoxymethylpentane,2,5-dimethyl-3-butylcarbonyl-3′-methoxymethylpentane,2,5-dimethyl-3-i-butylcarbonyl-1′-methoxymethylcyclohexyl.2,5-dimethyl-3-pentylcarbonyl-3′-methoxymethylpentane,2,5-dimethyl-3-i-pentylcarbonyl-3′-methoxymethylpentane,2,5-dimethyl-3-neopentylcarbonyl-3′-methoxymethylpentane,2,5-dimethyl-3-hexhylcarbonyl-3′-methoxymethylpentane,2,5-dimethyl-3-2-ethylhexylcarbonyl-3′-methoxymethylpentanel,2,5-dimethyl-3-octylcarbonyl-3′-methoxymethylpentane,2,5-dimethyl-3-i-octylcarbonyl-3′-methoxymethylpentane, and2,5-dimethyl-3-i -nonylcarbonyl-3′-methoxymethylpentane.

In one embodiment, the solid titanium catalyst compound includes theinternal electron donor containing at least one ether group and at leastone ketone group, but does not include other internal electron donors.In another embodiment, the solid titanium catalyst compound includesother internal electron donor in addition to the internal electron donorcontaining at least one ether group and at least one ketone group. Forexample, when preparing the solid titanium catalyst component, otherinternal electron donor can be used/added in addition to the internalelectron donor containing at least one ether group and at least oneketone group.

Examples of other internal electron donors include oxygen-containingelectron donors such as organic acid esters Specific examples includediethyl butylmalonate, diethyl dibutylmalonate, diethyl1,2-cyclohexanedicarboxylate, di-2-ethylhexyl1,2-cyclohexanedicarboxylate, methyl benzoate, ethyl benzoate, propylbenzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenylbenzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate,ethyl ethylbenzoate, methyl anisate, ethyl anisate, ethylethoxybenzoate, diethyl phthalate, dipropyl phthalate, diisopropylphthalate, dibutyl phthalate, diisobutyl phthalate, dioctyl phthalate,diisononyl phthalate

The internal electron donors may be used individually or in combination.In employing the internal electron donor, they do not have to be useddirectly as starting materials, but compounds convertible to theelectron donors in the course of preparing the titanium catalystcomponents may also be used as the starting materials.

When making the solid titanium catalyst compound, epoxy compounds can beused. For example, a solid titanium catalyst component is prepared bycontacting a magnesium compound with an epoxy compound. The epoxycompounds include compounds having at least one epoxy group in the formof monomers, dimmers, oligomers and polymers. Examples of epoxycompounds include aliphatic epoxy compounds, alicyclic epoxy compounds,aromatic epoxy compounds, or the like. Examples of aliphatic epoxycompounds include halogenated aliphatic epoxy compounds, aliphatic epoxycompounds having a keto group, aliphatic epoxy compounds having an etherbond, aliphatic epoxy compounds having an ester bond, aliphatic epoxycompounds having a tertiary amino group, aliphatic epoxy compoundshaving a cyano group, or the like. Examples of alicyclic epoxy compoundsinclude halogenated alicyclic epoxy compounds, alicyclic epoxy compoundshaving a keto group, alicyclic epoxy compounds having an ether bond,alicyclic epoxy compounds having an ester bond, alicyclic epoxycompounds having a tertiary amino group, alicyclic epoxy compoundshaving a cyano group, or the like. Examples of aromatic epoxy compoundsinclude halogenated aromatic epoxy compounds, aromatic epoxy compoundshaving a keto group, aromatic epoxy compounds having an ether bond,aromatic epoxy compounds having an ester bond, aromatic epoxy compoundshaving a tertiary amino group, aromatic epoxy compounds having a cyanogroup, or the like.

Specific examples of epoxy compounds include epifluorohydrin,epichlorohydrin, epibromohydrin, hexafluoropropylene oxide,1,2-epoxy-4-fluorobutane, 1-(2,3-epoxypropyl)-4-fluorobenzene,1-(3,4-epoxybutyl)-2-fluorobenzene, 1-(2,3-epoxypropyl)-4-chlorobenzene,1-(3,4-epoxybutyl)-3-chlorobenzene, or the like. Specific examples ofhalogenated alicyclic epoxy compounds include 4-fluoro-1,2-cyclohexeneoxide, 6-chloro-2,3-epoxybicyclo[2.2.1]heptane, or the like. Specificexamples of halogenated aromatic epoxy compounds include 4-fluorostyreneoxide, 1-(1,2-epoxypropyl)-3-trifluorobenzene, or the like.

In one embodiment, when the solid titanium catalyst component is formed,a surfactant is used. The surfactant can contribute to many of thebeneficial properties of the solid titanium catalyst component andcatalyst system. General examples of surfactants include polymersurfactants, such as polyacrylates, polymethacrylates, polyalkylmethacrylates, and the like. A polyalkyl methacrylate is a polymer thatmay contain one or more methacrylate monomers, such as at least twodifferent methacrylate monomers, at least three different methacrylatemonomers, etc. Moreover, the acrylate and methacrylate polymers maycontain monomers other than acrylate and methacrylate monomers, so longas the polymer surfactant contains at least about 40% by weight acrylateand methacrylate monomers.

In one embodiment, non-ionic surfactants and/or anionic surfactants canbe used. Examples of non-ionic surfactants and/or anionic surfactantsinclude phosphate esters, alkyl sulfonates, aryl sulfonates, alkylarylsulfonates, linear alkyl benzene sulfonates, alkylphenols, ethoxylatedalcohols, carboxylic esters, fatty alcohols, fatty esters, fattyaldehydes, fatty ketones, fatty acid nitriles, benzene, naphthalene,anthracene, succinic anhydride, phthalic anhydride, rosin, terpene,phenol, or the like. In fact a number of anhydride surfactants areeffective. In some instances, the absence of an anhydride surfactantcauses the formation of very small catalyst support particles while theover use creates straw shaped material sometimes referred to as needles.

The solid titanium catalyst component can be formed by contacting themagnesium compound, the titanium compound, and the internal electrondonor by known methods used to prepare a highly active titanium catalystcomponent.

Several examples of the method of producing the solid titanium catalystcomponent are briefly described below.

(1) The magnesium based catalytic support optionally with the internalelectron donor, is reacted with the titanium compound in the liquidphase.

(2) The magnesium based catalytic support and the titanium compounds arereacted in the presence of the internal electron donor to precipitate asolid titanium complex.

(3) The reaction product obtained in (2) is further reacted with thetitanium compound.

(4) The reaction product obtained in (1) or (2) is further reacted withthe internal electron donor and the titanium compound.

(5) The product obtained in (1) to (4) is treated with a halogen, ahalogen compound or an aromatic hydrocarbon.

(6) A magnesium based catalytic support is reacted with the optionalinternal electron donor, the titanium compound and/or ahalogen-containing hydrocarbon.

(7) The magnesium based catalytic support is reacted with the titaniumcompound in the liquid phase, filtered and washed. The reaction productis further reacted with the internal electron donor and the titaniumcompound, then activated with additional titanium compound in an organicmedium.

In embodiments of making the solid titanium catalyst component accordingto examples (2), (3), (4) and (5), the magnesium based solution is mixedwith a titanium compound such as liquid titanium tetrahalide to form asolid precipitate in the optional presence of an auxiliary precipitant.A polycarboxylic acid ester may be added before, during or after theprecipitation of the solids and loaded on the solid.

The process of solids precipitation can be carried out by at least oneof three methods. One method involves mixing a titanium compound such asliquid titanium tetrahalide with magnesium based solution at atemperature in the range of about −40 degrees Celsius to about 0 degreesCelsius, and precipitating the solids while the temperature is raisedslowly to a range from about 30 degrees Celsius to about 120 degreesCelsius, such as from about 60 degrees Celsius to about 100 degreesCelsius. The second method involves adding a titanium compound dropwiseinto a magnesium based solution at low or room temperature toprecipitate out solids immediately. The third method involves adding afirst titanium compound dropwise into a magnesium based solution andmixing a second titanium compound with the magnesium support. In thesemethods, an internal electron donor can be desirably present in thereaction system. The internal electron donor can be added either afterthe magnesium based solution is obtained or after the magnesium basedcatalytic support Is formed. Alternatively auxiliary precipitants can beadded to form the magnesium based catalytic support.

The catalyst precursor can be formed in the following way. In a solventsuch as toluene, a magnesium and titanium containing solution is seenfollowing the addition of a halogenating agent such as TiCl₄ atrelatively cooler temperatures, such as −25 degrees Celsius until about0 degree Celsius. An oil phase is then formed, which can be dispersedinto the hydrocarbon phase that is stable until about 40 degreesCelsius. The resultant magnesium material becomes a semi-solid at thispoint and the particle morphology is now determined. The semi-solidconverts to a solid between about 40 degrees Celsius and about 80degrees Celsius.

To facilitate obtaining uniform solid particles, the process ofprecipitation can be carried out slowly. When the second method ofadding titanium halide dropwise at low or room temperature is applied,the process may take place over a period from about 1 hour to about 6hours. When the first method of raising the temperature in a slow manneris applied, the rate of temperature increase can range from about 4degrees Celsius to about 100 degrees Celsius per hour.

The solid precipitate is first separated from the mixture. In the solidprecipitate thus obtained may be entrained a variety of complexes andbyproducts, so that further treatment may in some instances benecessary. In one embodiment, the solid precipitate is treated with atitanium compound to substantially remove the byproducts from the solidprecipitate.

The solid precipitate can be washed with an inert diluent and thentreated with a titanium compound or a mixture of a titanium compound andan inert diluent. The titanium compound used in this treatment can beidentical to or different with the titanium compound used for formingthe solid precipitate. The amount of titanium compound used is fromabout 1 to about 20 moles, such as from about 2 to about 15 moles, permole of magnesium compound in the support. The treatment temperatureranges from about 50 degrees Celsius to about 150 degrees Celsius, suchas from about 60 degrees Celsius to about 100 degrees Celsius. If amixture of titanium tetrahalide and inert diluent is used to treat thesolid precipitate, the volume % of titanium tetrahalide in the treatingsolution is from about 10% to about 100%, the rest being an inertdiluent.

The treated solids can be further washed with an inert diluent to removeineffective titanium compounds and other byproducts. The inert diluentherein used can be hexane, heptane, octane, 1,2-dichloroethane, benzene,toluene, ethylbenzene, xylenes, and other hydrocarbons.

By treating the solid precipitate with the titanium compound andoptionally an inert diluent, the byproducts in the solid precipitate canbe removed from the solid precipitate. In one embodiment, the solidprecipitate is treated with the titanium compound and optionally aninert diluent about two times or more and five times or less.

By treating the solid precipitate with an inert diluent, a free titaniumcompound in the solid precipitate can be removed from the solidprecipitate. As a result, the resultant solid precipitate does notsubstantially contain a free titanium compound. In one embodiment, thesolid precipitate is treated repeatedly with an inert diluent until thefiltrate contains about 100 ppm or less of titanium. In anotherembodiment, the solid precipitate is treated repeatedly with an inertdiluent until the filtrate contains about 50 ppm or less of titanium. Inyet another embodiment, the solid precipitate is treated repeatedly withan inert diluent until the filtrate contains about 10 ppm or less oftitanium. In one embodiment, the solid precipitate is treated with aninert diluent about three times or more and seven times or less.

In one embodiment, particularly embodiments following example (2)described above, the solid catalyst component has the following chemicalcomposition: titanium, from about 0.5 to about 6.0 wt %; magnesium, fromabout 10 to about 25 wt %; halogen, from about 40 to about 70 wt %;internal electron donor, from about 1 to about 25 wt %; and optionallyinert diluent from about 0 to about 15 wt %.

The amounts of the ingredients used in preparing the solid titaniumcatalyst component may vary depending upon the method of preparation. Inone embodiment, from about 0.01 to about 5 moles of the internalelectron donor and from about 0.01 to about 500 moles of the titaniumcompound are used per mole of the magnesium compound used to make thesolid titanium catalyst component. In another embodiment, from about0.05 to about 2 moles of the internal electron donor and from about 0.05to about 300 moles of the titanium compound are used per mole of themagnesium compound used to make the solid titanium catalyst component.

In one embodiment, in the solid titanium catalyst component, the atomicratio of halogen/titanium is from about 4 to about 200; the internalelectron donor/titanium mole ratio is from about 0.01 to about 10; andthe magnesium/titanium atomic ratio is from about 1 to about 100. Inanother embodiment, in the solid titanium catalyst component, the atomicratio of halogen/titanium is from about 5 to about 100; the internalelectron donor/titanium mole ratio is from about 0.2 to about 6; and themagnesium/titanium atomic ratio is from about 2 to about 50.

The resulting solid titanium catalyst component generally contains amagnesium halide of a smaller crystal size than commercial magnesiumhalides and usually has a specific surface area of at least about 50m²/g, such as from about 60 to 1,000 m²/g, or from about 100 to 800m²/g. Since, the above ingredients are unified to form an integralstructure of the solid titanium catalyst component, the composition ofthe solid titanium catalyst component does not substantially change bywashing with, for example, hexane.

The solid titanium catalyst component may be used after being dilutedwith an inorganic or organic compound such as a silicon compound, analuminum compound, or the like.

Methods of preparing solid titanium catalyst components, which can beused in the subject innovation, are described in U.S. PatentPublications and U.S. Pat. Nos. 4,771,023; 4,784,983; 4,829,038;4,861,847; 4,990,479; 5,177,043; 5,194,531; 5,244,989; 5,438,110;5,489,634; 5,576,259; 5,767,215; 5,773,537; 5,905,050; 6,323,152;6,437,061; 6,469,112; 6,962,889; 7,135,531; 7,153,803; 7,271,119;2004242406; 2004/0242407; and 2007/0021573 which are hereby incorporatedby reference in this regard.

The catalyst system may contain at least one organoaluminum compound inaddition to the solid titanium catalyst component. Compounds having atleast one aluminum-carbon bond in the molecule can be used as theorganoaluminum compound. Examples of organoaluminum compounds includecompounds of the following Formula (III)

R_(m)AIX_(p)  (11)

In Formula (III), each R independently represents a hydrocarbon groupusually having 1 to about 15 carbon atoms, or from 1 to about 4 carbonatoms; X represents a halogen atom, m<3, 0≦p<3, and m+p=3.

Specific examples of the organoaluminum compounds represented by Formula(III) include trialkyl aluminums such as triethyl aluminum and tributylaluminum; trialkenyl aluminums such as triisoprenyl aluminum; dialkylaluminum alkoxides such as diethyl aluminum ethoxide and dibutylaluminum butoxide; alkyl aluminum sesquialkoxides such as ethyl aluminumsesquiethoxide and butyl aluminum sesquibutoxide; partially alkoxylatedalkyl aluminums having an average composition represented by R¹¹_(2.5)Al(OR¹²)_(0.5); dialkyl aluminum halides such as diethyl aluminumchloride, dibutyl aluminum chloride and diethyl aluminum bromide; alkylaluminum sesquihalides such as ethyl aluminum sesquichloride, butylaluminum sesquichloride and ethyl aluminum sesquibromide; partiallyhalogenated alkyl aluminums, for example alkyl aluminum dihalides suchas ethyl aluminum dichloride, propyl aluminum dichloride and butylaluminum dibromide; dialkyl aluminum hydrides such as diethyl aluminumhydride and dibutyl aluminum hydride; other partially hydrogenated alkylaluminum, for example alkyl aluminum dihyrides such as ethyl aluminumdihydride and propyl aluminum dihydride; and partially alkoxylated andhalogenated alkyl aluminums such as ethyl aluminum ethoxychloride, butylaluminum butoxychloride, and ethyl aluminum ethoxybromide.

The organoaluminum compound catalyst component is used in the catalystsystem of the subject innovation in an amount that the mole ratio ofaluminum to titanium (from the solid catalyst component) is from about 5to about 1,000. In another embodiment, the mole ratio of aluminum totitanium in the catalyst system is from about 10 to about 700. In yetanother embodiment, the mole ratio of aluminum to titanium in thecatalyst system is from about 25 to about 400.

The catalyst system may contain at least one organosilicon compound inaddition to the solid titanium catalyst component. This organosiliconcompound is sometimes termed an external electron donor. Theorganosilicon compound contains silicon having at least one hydrocarbonligand (hydrocarbon group). General examples of hydrocarbon groupsinclude alkyl groups, cycloalkyl groups, (cycloalkyl)methylene groups,alkene groups, aromatic groups, and the like.

The organosilicon compound, when used as an external electron donorserving as one component of a Ziegler-Natta catalyst system for olefinpolymerization, contributes to the ability to obtain a polymer (at leasta portion of which is polyolefin) having a controllable molecular weightdistribution and controllable crystallinity while retaining highperformance with respect to catalytic activity.

The organosilicon compound is used in the catalyst system in an amountthat the mole ratio of the organoaluminum compound to the organosiliconcompound is from about 2 to about 90. In another embodiment, the moleratio of the organoaluminum compound to the organosilicon compound isfrom about 5 to about 70. In yet another embodiment, the mole ratio ofthe organoaluminum compound to the organosilicon compound is from about7 to about 35.

In one embodiment, the organosilicon compound is represented by Formula(IV)

R_(n)Si(OR′)_(4-n)  (IV)

wherein each R and R′ independently represent a hydrocarbon group, and nis 0≦n≦4.

Specific examples of the organosilicon compound of Formula (V) includetrimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane,dimethyldiethoxysilane, diisopropyldimethoxysilane,diisobutyldimethoxysilane, t-butylmethyldimethoxysilane,t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane,dicyclopentyldimethoxysilane, diphenyldimethoxysilane,phenylmethyldimethoxysilane, diphenyldiethoxysilane,bis-o-tolyidimethoxysilane, bis-m-tolyldimethoxysilane,bis-p-tolyidimethoxysilane, bis-p-totyidiethoxysilane,bisethylphenyldimethoxysilane, dicyclohexyldimethoxysilane,cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane,ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane,methyltrimethoxysilane, n-propyltriethoxysilane, decyltrimethoxysilane,decyltriethoxysilane, phenyltrimethoxysilane,gamma-chloropropyltrimethoxysilane, methyltriethoxysilane,ethyltriethoxysilane, vinyltriethoxysilane, t-butyltriethoxysilane,n-butyltriethoxysilane, iso-butyltriethoxysilane, phenyltriethoxysilane,gamma-aminopropyltriethoxysilane, chlorotriethoxysilane,ethyltriisopropoxysilane, vinyltributoxysilane,cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane,2-norbornanetrimethoxysilane, 2-norboranetriethoxysilane,2-norbornanemethyldimethoxysilane, ethyl silicate, butyl silicate,trimethylphenoxysilane, and methyltriallyloxysilane,

In another aspect of the subject innovation, the organosilicon compoundis represented by Formula (V)

SiRR′_(m)(OR″)_(3-m)  (V)

In the above Formula (V), 0≦m≦3, such as 0≦m≦2; and each R independentlyrepresents a cyclic hydrocarbon or substituted cyclic hydrocarbon group.Specific examples of the group R include cyclopropyl, cyclobutyl,cyclopentyl, 2-methylcyclopentyl, 3-methylcyclopentyl,2-ethylcyclopentyl, 3-propylcyclopentyl, 3-isopropylcyclopentyl,3-butylcyclopentyl, 3-tertiary butyl cyclopentyl,2,2-dimethylcyclopentyl, 2,3-dimethylcyclopentyl,2,5-dimethylcyclopentyl, 2,2,5-trimethylcyclopentyl,2,3,4,5-tetramethylcyclopentyl, 2,2,5,5-tetramethylcyclopentyl,1-cyclopentylpropyl, 1-methyl-1-cyclopentylethyl, cyclopentenyl,2-cyclopentenyl, 3-cyclopentenyl, 2-methyl-1-cyclopentenyl,2-methyl-3-cyclopentenyl, 3-methyl-3-cyclopentenyl,2-ethyl-3-cyclopentenyl, 2,2-dimethyl-3-cyclopentenyl,2,5-dimethyl-3-cyclopentenyl, 2,3,4,5-tetramethyl-3-cyclopentenyl,2,2,5,5-tetramethyl-3-cyclopentenyl, 1,3-cyclopentad ienyl,2,4-cyclopentadienyl, 1,4-cyclopentadienyl,2-methyl-1,3-cyclopentadienyl, 2-methyl-2,4-cyclopentadienyl,3-methyl-2,4-cyclopentadienyl, 2-ethyl-2,4-cyclopentadienyl,2-dimethyl-2,4-cyclopentadienyl, 2,3-dimethyl-2,4-cyclopentadienyl,2,5-dimethyl-2,4-cyclopentadienyl,2,3,4,5-tetramethyl-2,4-cyclopentadienyl, indenyl, 2-methylindenyl,2-ethylindenyl, 2-indenyl, 1-methyl-2-indenyl, 1,3-dimethyl-2-indenyl,indanyl, 2-methylindanyl, 2-indanyl, 1,3-dimethyl-2-indanyl,4,5,6,7-tetrahydroindenyl, 4,5,6,7-tetrahydro-2-indenyl,4,5,6,7-tetrahydro-1-methyl-2-indenyl,4,5,6,7-tetrahydro-1,3-dimethyl-2-indenyl, fluorenyl groups, cyclohexyl,methylcyclohexyls, ethylcyclohexyls, propylcyclohexyls,isopropylcyclohexyls, n-butylcyclohexyls, tertiary-butyl cyclohexyls,dimethylcyclohexyls, and trimethylcyclohexyls.

In Formula (V), R′ and R″ are identical or different and each representsa hydrocarbon. Examples of R′ and R″ are alkyl, cycloalkyl, aryl andaralkyl groups having 3 or more carbon atoms. Furthermore, R and R′ maybe bridged by an alkyl group, etc. General examples of organosiliconcompounds are those of Formula (V) in which R is a cyclopentyl group, R′is an alkyl group such as methyl or a cyclopentyl group, and R¹⁸ is analkyl group, particularly a methyl or ethyl group.

Specific examples of organosilicon compounds of Formula (V) includetrialkoxysilanes such as cyclopropyltrimethoxysilane,cyclobutyltrimethoxysilane, cyclopentyltrimethoxysilane,2-methylcyclopentyltrimethoxysilane,2,3-dimethylcyclopentyltrimethoxysilane,2,5-dimethylcyclopentyltrimethoxysilane, cyclopentyltriethoxysilane,cyclopentenyltrimethoxysilane, 3-cyclopentenyltrimethoxysilane,2,4-cyclopentadienyltrimethoxysilane, indenyltrimethoxysilane andfluorenyltrimethoxysilane; dialkoxysilanes such asdicyclopentyldimethoxysilane, bis(2-methylcyclopentyl)dimethoxysilane,bis(3-tertiary butylcyclopentyl)dimethoxysilane,bis(2,3-dimethylcyclopentyl)dimethoxysilane,bis(2,5-dimethylcyclopentyl)dimethoxysilane,dicyclopentyldiethoxysilane, dicyclobutyldiethoxysilane,cyclopropylcyclobutyldiethoxysilane, dicyclopentenyidimethoxysilane,di(3-cyclopentenyl)dimethoxysilane,bis(2,5-dimethyl-3-cyclopentenyl)dimethoxysilane,di-2,4-cyclopentadienyldimethoxysilane,bis(2,5-dimethyl-2,4-cyclopentadienyl)dimethoxysilane,bis(1-methyl-1-cyclopentylethyl)dimethoxysilane,cyclopentylcyclopentenyldimethoxysilane,cyclopentylcyclopentadienyidimethoxysilane, diindenyldimethoxysilane,bis(1,3-dimethyl-2-indenyl)dimethoxysilane,cyclopentadienylindenyldimethoxysilane, difluorenyidimethoxysilane,cyclopentylfluorenyldimethoxysilane and indenylfluorenyldimethoxysilane;monoalkoxysilanes such as tricyclopentylmethoxysilane,tricyclopentenylmethoxysilane, tricyclopentadienylmethoxysilane,tricyclopentylethoxysilane, dicyclopentylmethylmethoxysilane,dicyclopentylethylmethoxysilane, dicyclopentylmethylethoxysilane,cyclopentyldimethylmethoxysilane, cyclopentyldiethylmethoxysilane,cyclopentyldimethylethoxysilane,bis(2,5-dimethylcyclopentyl)cyclopentylmethoxysilane,dicyclopentylcyclopentenylmethoxysilane,dicyclopentylcyclopentadienylmethoxysilane anddiindenylcyclopentylmethoxysilane; andethylenebis-cyclopentyldimethoxysilane.

Polymerization of olefins in accordance with the subject innovation iscarried out in the presence of the catalyst system described above.Generally speaking, olefins are contacted with the catalyst systemdescribed above under suitable conditions to form desired polymerproducts. In one embodiment, preliminary polymerization described belowis carried out before the main polymerization. In another embodiment,polymerization is carried out without preliminary polymerization. In yetanother embodiment, the formation of copolymer is carried out using atleast two polymerization zones.

In preliminary polymerization, the solid titanium catalyst component isusually employed in combination with at least a portion of theorganoaluminum compound. This may be carried out in the presence of partor the whole of the organosilicon compound (external electron donor).The concentration of the catalyst system used in the preliminarypolymerization may be much higher than that in the reaction system ofthe main polymerization.

In preliminary polymerization, the concentration of the solid titaniumcatalyst component in the preliminary polymerization is usually fromabout 0.01 to about 200 millimoles, preferably from about 0.05 to about100 millimoles, calculated as titanium atoms per liter of an inerthydrocarbon medium described below. In one embodiment, the preliminarypolymerization is carried out by adding an olefin and the above catalystsystem ingredients to an inert hydrocarbon medium and reacting theolefin under mild conditions.

Specific examples of the inert hydrocarbon medium include aliphatichydrocarbons such as propane, butane, pentane, hexane, heptane, octane,decane, dodecane and kerosene; alicyclic hydrocarbons such ascyclopentane, cyclohexane and methylcyclopentane; aromatic hydrocarbonssuch as benzene, toluene and xylene; halogenated hydrocarbons such asethylene chloride and chlorobenzene; and mixtures thereof. In thesubject innovation, a liquid olefin may be used in place of part or thewhole of the inert hydrocarbon medium.

The olefin used in the preliminary polymerization may be the same as, ordifferent from, an olefin to be used in the main polymerization.

The reaction temperature for the preliminary polymerization issufficient for the resulting preliminary polymer to not substantiallydissolve in the inert hydrocarbon medium. In one embodiment, thetemperature is from about −20 degrees Celsius to about 100 degreesCelsius. In another embodiment, the temperature is from about −10degrees Celsius to about 80 degrees Celsius. In yet another embodiment,the temperature is from about 0 degrees Celsius to about 40 degreesCelsius.

Optionally, a molecular-weight controlling agent, such as hydrogen, maybe used in the preliminary polymerization. The molecular weightcontrolling agent is used in such an amount that the polymer obtained bythe preliminary polymerization has an intrinsic viscosity, measured indecalin at 135 degrees Celsius, of at least about 0.2 dl/g, andpreferably from about 0.5 to 10 dl/g.

In one embodiment, the preliminary polymerization is desirably carriedout so that from about 0.1 g to about 1,000 g of a polymer forms pergram of the titanium catalyst component of the catalyst system. Inanother embodiment, the preliminary polymerization is desirably carriedout so that from about 0.3 g to about 500 g of a polymer forms per gramof the titanium catalyst component. If the amount of the polymer formedby the preliminary polymerization is too large, the efficiency ofproducing the olefin polymer in the main polymerization may sometimesdecrease, and when the resulting olefin polymer is molded into a film oranother article, fish eyes tend to occur in the molded article. Thepreliminary polymerization may be carried out batchwise or continuously.

After the preliminary polymerization conducted as above, or withoutperforming any preliminary polymerization, the main polymerization of anolefin is carried out in the presence of the above-described olefinpolymerization catalyst system formed from the solid titanium catalystcomponent, the organoaluminum compound and the organosilicon compound(external electron donor).

Examples of olefins that can be used in the main polymerization arealpha-olefins having 2 to 20 carbon atoms such as ethylene, propylene,1-butene, 4-methyl-1-pentene, 1-pentene, 1-octene, 1-hexene,3-methyl-1-pentene, 3-methyl-1-butene, 1-decene, 1-tetradecene,1-eicosene, and vinylcyclohexane. In the process of the subjectinnovation, these alpha-olefins may be used individually or in anycombination.

In one embodiment, propylene or 1-butene is homopolymerized, or a mixedolefin containing propylene or 1-butene as a main component iscopolymerized. When the mixed olefin is used, the proportion ofpropylene or 1-butene as the main component is usually at least about 50mole %, preferably at least about 70 mole %.

By performing the preliminary polymerization, the catalyst system in themain polymerization can be adjusted in the degree of activity. Thisadjustment tends to result in a powdery polymer having a high bulkdensity. Furthermore, when the preliminary polymerization is carriedout, the particle shape of the resulting polymer becomes spherical, andin the case of slurry polymerization, the slurry attains excellentcharacteristics while in the case of gas phase polymerization, thepolymer seed bed attains excellent characteristics. Furthermore, inthese embodiments, a polymer having a high stereoregularity index can beproduced with a high catalytic efficiency by polymerizing analpha-olefin having at least about 3 carbon atoms. Accordingly, whenproducing the propylene copolymer, the resulting copolymer powder or thecopolymer becomes easy to handle.

In the homopolymerization or copolymerization of these olefins, apolyunsaturated compound such as a conjugated diene or a non-conjugateddiene may be used as a comonomer. Examples of comonomers includestyrene, butadiene, acrylonitrile, acrylamide, alpha-methyl styrene,chlorostyrene, vinyl toluene, divinyl benzene, diallylphthalate, alkylmethacrylates and alkyl acrylates.

In one embodiment, the comonomers include thermoplastic and elastomericmonomers.

In the process of the subject innovation, the main polymerization of anolefin is carried out usually in the gaseous or liquid phase.

In one embodiment, polymerization (main polymerization) employs acatalyst system containing the titanium catalyst component in an amountfrom about 0.001 to about 0.75 millimole calculated as Ti atom per literof the volume of the polymerization zone, the organoaluminum compound inan amount from about 1 to about 2,000 moles per mole of titanium atomsin the titanium catalyst component, and the organosilicon compound(external donor) in an amount from about 0.001 to about 10 molescalculated as Si atoms in the organosilicon compound per mol of themetal atoms in the organoaluminum compound. In another embodiment,polymerization employs a catalyst system containing the titaniumcatalyst component in an amount from about 0.005 to about 0.5 millimolecalculated as Ti atom per liter of the volume of the polymerizationzone, the organoaluminum compound in an amount from about 5 to about 500moles per mole of titanium atoms in the titanium catalyst component, andthe organosilicon compound in an amount from about 0.01 to about 2 molescalculated as Si atoms in the organosilicon compound per mol of themetal atoms in the organoaluminum compound. In yet another embodiment,polymerization employs a catalyst system containing the organosiliconcompound in an amount from about 0.05 to about 1 mole calculated as Siatoms in the organosilicon compound per mol of the metal atoms in theorganoaluminum compound.

When the organoaluminum compound and the organosilicon compound are usedpartially in the preliminary polymerization, the catalyst systemsubjected to the preliminary polymerization is used together with theremainder of the catalyst system components. The catalyst systemsubjected to the preliminary polymerization may contain the preliminarypolymerization product.

The use of hydrogen at the time of polymerization promotes andcontributes to control of the molecular weight of the resulting polymer,and the polymer obtained may have a high melt flow rate. In this case,the stereoregularity index of the resulting polymer and the activity ofthe catalyst system are increased according to the methods of thesubject innovation.

In one embodiment, the polymerization temperature is from about 20degrees Celsius to about 200 degrees Celsius. In another embodiment, thepolymerization temperature is from about 50 degrees Celsius to about 180degrees Celsius. In one embodiment, the polymerization pressure istypically from about atmospheric pressure to about 100 kg/cm². Inanother embodiment, the polymerization pressure is typically from about2 kg/cm² to about 50 kg/cm². The main polymerization may be carried outbatchwise, semi-continuously or continuously. The polymerization mayalso be carried out in two or more stages under different reactionconditions.

The olefin polymer so obtained may be a homopolymer, a random copolymer,a block copolymer or an impact copolymer. The impact copolymer containsan intimate mixture of a polyolefin homopolymer and a polyolefin rubber.Examples of polyolefin rubbers include ethylene propylene rubbers (EPR)such as ethylene propylene methylene copolymer rubber (EPM) and ethylenepropylene diene methylene terpolymer rubber (EPDM).

The olefin polymer obtained by using the catalyst system has a verysmall amount of an amorphous polymer component and therefore a smallamount of a hydrocarbon-soluble component. Accordingly, a film moldedfrom this resultant polymer has low surface tackiness.

The polyolefin obtained by the polymerization process is excellent inparticle size distribution, particle diameter and bulk density, and thecopolyolefin obtained has a narrow composition distribution. In animpact copolymer, excellent fluidity, low temperature resistance, and adesired balance between stiffness and elasticity can be obtained.

In one embodiment, propylene and an alpha-olefin having 2 or from about4 to about 20 carbon atoms are copolymerized in the presence of thecatalyst system described above. The catalyst system may be onesubjected to the preliminary polymerization described above. In anotherembodiment, propylene and an ethylene rubber are formed in two reactorscoupled in series to form an impact copolymer.

The alpha-olefin having 2 carbon atoms is ethylene, and examples of thealpha-olefins having about 4 to about 20 carbon atoms are 1-butene,1-pentene, 4-methyl-1-pentene, 1-octene, 1-hexene, 3-methyl-1-pentene,3-methyl-1-butene, 1-decene, vinylcyclohexane, 1-tetradecene, and thelike.

In the main polymerization, propylene may be copolymerized with two ormore such alpha-olefins. For example, it is possible to copolymerizepropylene with ethylene and 1-butene. In one embodiment, propylene iscopolymerized with ethylene, 1-butene, or ethylene and 1-butene.

Block copolymerization of propylene and another alpha-olefin may becarried out in two stages. The polymerization in a first stage may bethe homopolymerization of propylene or the copolymerization of propylenewith the other alpha-olefin. In one embodiment, the amount of themonomers polymerized in the first stage is from about 50 to about 95% byweight. In another embodiment, the amount of the monomers polymerized inthe first stage is from about 60 to about 90% by weight. In the subjectinnovation, this first stage polymerization may, as required be carriedout in two or more stages under the same or different polymerizationconditions.

In one embodiment, the polymerization in a second stage is desirablycarried out such that the mole ratio of propylene to the otheralpha-olefin(s) is from about 10/90 to about 90/10. In anotherembodiment, the polymerization in a second stage is desirably carriedout such that the mole ratio of propylene to the other alpha-olefin(s)is from about 20/80 to about 80/20. In yet another embodiment, thepolymerization in a second stage is desirably carried out such that themole ratio of propylene to the other alpha-olefin(s) is from about 30/70to about 70/30. Producing a crystalline polymer or copolymer of anotheralpha-olefin may be provided in the second polymerization stage.

The propylene copolymer so obtained may be a random copolymer or theabove-described block copolymer. This propylene copolymer typicallycontains from about 7 to about 50 mole % of units derived from thealpha-olefin having 2 or from about 4 to about 20 carbon atoms. In oneembodiment, a propylene random copolymer contains from about 7 to about20 mole % of units derived from the alpha-olefin having 2 or from about4 to about 20 carbon atoms. In another embodiment, the propylene blockcopolymer contains from about 10 to about 50 mole % of units derivedfrom the alpha-olefin having 2 or 4-20 carbon atoms.

In another one embodiment, copolymers made with the catalyst systemcontain from about 50% to about 99% by weight poly-alpha-olefins andfrom about 1% to about 50% by weight comonomers (such as thermoplasticor elastomeric monomers). In another embodiment, copolymers made withthe catalyst system contain from about 75% to about 98% by weightpoly-alpha-olefins and from about 2% to about 25% by weight comonomers.

It should be understood that where there is no reference to thepolyunsaturated compound that can be used, the method of polymerization,the amount of the catalyst system and the polymerization conditions, thesame description as the above embodiments are applicable.

The catalysts/methods of the subject innovation can in some instanceslead to the production of poly-alpha-olefins having xylene solubles (XS)from about 0.5% to about 10%. In another embodiment, poly-alpha-olefinshaving xylene solubles (XS) from about 1.5% to about 6% are produced inaccordance with the subject innovation. XS refers to the percent ofsolid polymer that dissolves into xylene. A low XS % value generallycorresponds to a highly isotactic polymer (i.e., higher crystallinity),whereas a high XS % value generally corresponds to a low isotacticpolymer.

In one embodiment, the catalyst efficiency (measured as kilogram ofpolymer produced per gram of catalyst) of the catalyst system of thesubject innovation is at least about 30. In another embodiment, thecatalyst efficiency of the catalyst system of the subject innovation isat least about 60.

The catalysts/methods of the subject innovation can in some instanceslead to the production of poly-alpha-olefins having melt flow indexes(MFI) from about 0.1 to about 100. The MFI is measured according to ASTMstandard D 1238. In another embodiment, poly-alpha-olefins having an MFIfrom about 5 to about 30 are produced in accordance with the subjectinnovation. In one embodiment, an impact polypropylene-ethylenepropylenerubber product has an MFI from about 4 to about 10. In anotherembodiment, an impact polypropylene-ethylenepropylene rubber product hasan MFI from about 5 to about 9. In some instances a relatively high MFIindicates that a relatively high catalyst efficiency is obtainable.

The catalysts/methods of the subject innovation can in some instanceslead to the production of poly-alpha-olefins having bulk densities (BD)of at least about 0.3 cc/g. In another embodiment, poly-alpha-olefinshaving a BD of at least about 0.4 cc/g are produced in accordance withthe subject innovation.

In one embodiment, an impact polypropylene-ethylenepropylene rubberproduct having a BD of at least about 0.3 cc/g is produced in accordancewith the subject innovation. In another embodiment, an impactpolypropylene-ethylenepropylene rubber product having a BD of at leastabout 0.4 cc/g is produced in accordance with the subject innovation.

The catalysts/methods of the subject innovation lead to the productionof poly-alpha-olefins having a relatively narrow molecular weightdistribution. In one embodiment, the Mw/Mn of a polypropylene polymermade with the catalyst system is from about 2 to about 6. In anotherembodiment, the Mw/Mn of a polypropylene polymer made with the catalystsystem is from about 3 to about 5.

The subject innovation can lead to the production of a propylene blockcopolymer and impact copolymers including polypropylene based impactcopolymers having one or more of excellent melt-flowability,moldability, desirable balance between rigidity and elasticity, goodstereospecific control, good control over polymer particle size, shape,size distribution, and molecular weight distribution, and impactstrength with a high catalytic efficiency and/or good operability.Employing the catalyst systems containing the solid titanium catalystcomponent according to the subject innovation yields catalystssimultaneously having high catalytic efficiency and one or more ofexcellent melt-flowability, extrudability, moldability,rigidity-elasticity, impact strength and impact strength.

Examples of systems for polymerizing olefins are now described.Referring to FIG. 1, a high level schematic diagram of a system 10 forpolymerizing olefins is shown. Inlet 12 is used to introduce into areactor 14 catalyst system components, olefins, optional comonomers,hydrogen gas, fluid media, pH adjusters, surfactants, and any otheradditives. Although only one inlet is shown, many often are employed.Reactor 14 is any suitable vehicle that can polymerize olefins. Examplesof reactors 14 include a single reactor, a series of two or morereactors, slurry reactors, fixed bed reactors, gas phase reactors,fluidized gas reactors, loop reactors, multizone circulating reactors,and the like. Once polymerization is complete, or as polyolefins areproduced, the polymer product is removed from the reactor 14 via outlet16 which leads to a collector 18. Collector 18 may include downstreamprocessing, such as heating, extrusion, molding, and the like.

Referring to FIG. 2, a schematic diagram of a multizone circulatingreactor 20 that can be employed as the reactor 14 in FIG. 1 or reactor44 in FIG. 3 for making polyolefins. The multizone circulating reactor20 substitutes a series of separate reactors with a single reactor loopthat permits different gas phase polymerization conditions in the twosides due to use of a liquid barrier. In the multizone circulatingreactor 20, a first zone starts out rich in olefin monomer, andoptionally one or more comonomers. A second zone is rich in hydrogengas, and a high velocity gas flow divides the growing resin particlesout loosely. The two zones produce resins of different molecular weightand/or monomer composition. Polymer granules grow as they circulatearound the loop, building up alternating layers of each polymer fractionin an onion like fashion. Each polymer particle constitutes an intimatecombination of both polymer fractions.

In operation, the polymer particles pass up through the fluidizing gasin an ascending side 24 of the loop and come down through the liquidmonomer on a descending side 26. The same or different monomers (andagain optionally one or more comonomers) can be added in the two reactorlegs. The reactor uses the catalyst systems described above.

In the liquid/gas separation zone 30, hydrogen gas is removed to cooland recirculate. Polymer granules are then packed into the top of thedescending side 26, where they then descend. Monomers are introduced asliquids in this section. Conditions in the top of the descending side 26can be varied with different combinations and/or proportions of monomersin successive passes.

Referring to FIG. 3, a high level schematic diagram of another system 40for polymerizing olefins is shown. This system is ideally suited to makeimpact copolymer. A reactor 44, such as a single reactor, a series ofreactors, or the multizone circulating reactor is paired with a gasphase or fluidized bed reactor 48 downstream containing the catalystsystems described above to make impact copolymers with desirable impactto stiffness balance or greater softness than are made with conventionalcatalyst systems. Inlet 42 is used to introduce into the reactor 44catalyst system components, olefins, optional comonomers, hydrogen gas,fluid media, pH adjusters, surfactants, and any other additives.Although only one inlet is shown, many often are employed. Throughtransfer means 46 the polyolefin made in the first reactor 44 is sent toa second reactor 48. Feed 50 is used to introduce catalyst systemcomponents, olefins, optional comonomers, fluid media, and any otheradditives. The second reactor 48 may or may not contain catalyst systemcomponents. Again, although only one inlet is shown, many often areemployed. Once the second polymerization is complete, or as impactcopolymers are produced, the polymer product is removed from the secondreactor 48 via outlet 52 which leads to a collector 54. Collector 54 mayinclude downstream processing, such as heating, extrusion, molding, andthe like. At least one of the first reactor 44 and second reactor 48contains catalyst systems in accordance with the innovation.

When making an impact copolymer, polypropylene can be formed in thefirst reactor while an ethylene propylene rubber can be formed in thesecond reactor. In this polymerization, the ethylene propylene rubber inthe second reactor is formed with the matrix (and particularly withinthe pores) of the polypropylene formed in the first reactor.Consequently, an intimate mixture of an impact copolymer is formed,wherein the polymer product appears as a single polymer product. Such anintimate mixture cannot be made by simply mixing a polypropylene productwith an ethylene propylene rubber product.

Although not shown in any of the figures, the systems and reactors canbe controlled, optionally with feedback based on continuous orintermittent testing, using a processor equipped with an optional memoryand controllers. For example, a processor may be connected to one ormore of the reactors, inlets, outlets, testing/measuring systems coupledwith the reactors, and the like to monitor and/or control thepolymerization process, based on preset data concerning the reactions,and/or based on testing/measuring data generated during a reaction. Thecontroller may control valves, flow rates, the amounts of materialsentering the systems, the conditions (temperature, reaction time, pH,etc.) of the reactions, and the like, as instructed by the processor.The processor may contain or be coupled to a memory that contains dataconcerning various aspects of the polymerization process and/or thesystems involved in the polymerization process.

The following examples illustrate the subject innovation. Unlessotherwise indicated in the following examples and elsewhere in thespecification and claims, all parts and percentages are by weight, alltemperatures are in degrees Celsius, and pressure is at or nearatmospheric pressure.

Example 1

Anhydrous magnesium chloride (3.3 g), phthalic anhydride (0.8 g),toluene (50.92 g), epichlorohydrin (6.41 g) and tributyl phosphate (6.70g) are introduced into a 250 ml Buchi reactor under nitrogen. Themixture is heated for two hours while agitating at 400 rpm at 60 degreesCelsius. The reaction mixture is then cooled to −30 degrees Celsius and37.75 ml of TiCl₄ is added slowly while maintaining the reactortemperature below −26 degrees Celsius. After the addition, the agitationrate is reduced to 200 rpm and the temperature is ramped from −26degrees Celsius to 0 degree Celsius in one hour then 0 degree Celsius to85 degrees Celsius in one hour.

The mixture is held at 85 degrees Celsius for 30 minute then 1.1 g of9-(n-butylcarbonyl)-9′-methoxymethylfluorene is added (mother liquoraddition). The mixture is stirred at 85 degrees Celsius for one hourthen filtered. The solids are re-suspended in 38 ml of toluene and 0.43g of 9-(n-butylcarbonyl)-9′-methoxymethylfluorene is added to thereactor (toluene addition). The mixture is agitated for one hour at 85degrees Celsius and 200 rpm. After filtration and wash twice with 65 mltoluene, the mixture is left over night in toluene under N₂.

After filtering off the toluene, 66.25 ml of 10 vol % TiCl₄ in tolueneis added, and then heated to and held at 95 degrees Celsius with 400 rpmagitation for one hour (1st activation addition). The solids arefiltered then re-suspended in 66.25 ml of 10 vol % TiCl₄ in toluene. Themixture is held at 110 degrees Celsius for thirty minutes after whichthe solids are once again filtered. This act is repeated two more times.The final catalyst is washed four times with 65 ml of hexane thendischarged from the reactor in hexane.

Propylene Polymerization is performed in a 3.4 liter reactor. Thereactor is purged at 100 degrees Celsius under nitrogen for one hour. Atroom temperature 1.5 ml of 25-wt % triethyl aluminum in heptane is addedinto the reactor. Then 1.0 ml of 0.0768 M solution of cyclohexyl methyldimethoxy silane followed by 1 ml of 1-wt % catalyst slurry are addedinto the reactor. The reactor is pressurized with H₂ to 3.5 psig thencharged with 1500 ml propylene. The reactor is heated to then held at 70degrees Celsius for one hour. At the end of the reaction, the reactor isvented and the polymer is recovered.

The characteristics of polymer products and processes are summarized inTable 1. CE refers to catalytic efficiency to produce polypropylene(PP), XS refers to xylene solubles, and MFI refers to melt flow index.

TABLE 1 Yield CE XS MFI Example g PP kg PP/g catalyst wt % dg/min 1 50250.2 5.1 7.0

Example 2

The catalyst is synthesized under same conditions as Example 1 except1.2 g of 9-(n-butylcarbonyl)-9′-methoxymethylfluorene is added in thetoluene addition stage and 0.3 g of9-(n-butylcarbonyl)-9′-methoxymethylfluorene is added in the 1stactivation stage.

Propylene polymerization is the same as in Example 1. Thecharacteristics of polymer products and processes are summarized inTable 2.

TABLE 2 Yield CE XS MFI Example g PP kg PP/g catalyst wt % dg/min 2 44244.2 4.8 8.8

Example 3

The catalyst is synthesized under same conditions as Example 1 except0.4 g of diisooctylphthalate is added in the mother liquor additionstage, 1.2 g of 9-(n-butylcarbonyl)-9′-methoxymethylfluorene is added inthe toluene addition stage and 0.3 g of diisooctylphthalate is added inthe 1st activation stage.

Propylene polymerization is the same as in Example 1. Thecharacteristics of polymer products and processes are summarized inTable 3.

TABLE 3 Yield CE XS MFI Example g PP kg PP/g catalyst wt % dg/min 3 40740.7 4.3 6.3

Example 4

The catalyst is synthesized under same conditions as Example 1 except1.36 g of 9-(i-nonylcarbonyl)-9′-methoxymethylfluorene is added in themother liquor addition stage, 0.53 g of9-(i-nonylcarbonyl)-9′-methoxymethylfluorene is added in the tolueneaddition stage and no donor is added in the 1st activation stage.

Propylene polymerization is the same as in Example 1. Thecharacteristics of polymer products and processes are summarized inTable 4.

TABLE 4 Yield CE XS MFI Example g PP kg PP/g catalyst wt % dg/min 4 51551.5 4.8 2.9

Example 5

The catalyst is synthesized under same conditions as Example 1 except1.36 g of 9-(i-nonylcarbonyl)-9′-methoxymethylfluorene is added in themother liquor addition stage, 0.53 g of9-(i-nonylcarbonyl)-9′-methoxymethylfluorene is added in the tolueneaddition stage and 0.3 g of 9-(i-nonylcarbonyl)-9′-methoxymethylfluoreneis added in the 1st activation stage.

Propylene polymerization is the same as in Example 1. Thecharacteristics of polymer products and processes are summarized inTable 5.

TABLE 5 Yield CE XS MFI Example g PP kg PP/g catalyst wt % dg/min 5 61361.3 4.8 4.9

Example 6

The catalyst is synthesized under same conditions as Example 4 exceptthe 1st activation stage is hold at 105 degrees Celsius.

Propylene polymerization is the same as in Example 1. Thecharacteristics of polymer products and processes are summarized inTable 6.

TABLE 6 Yield CE XS MFI Example g PP kg PP/g catalyst wt % dg/min 6 49949.9 4.2 2.4

Example 7

The catalyst is synthesized under same conditions as Example 5 exceptthe 1st activation stage is hold at 105 degrees Celsius.

Propylene polymerization is the same as in Example 1. Thecharacteristics of polymer products and processes are summarized inTable 7.

TABLE 7 Yield CE XS MFI Example g PP kg PP/g catalyst wt % dg/min 7 56556.5 4.0 7.1

Example 8

The catalyst is synthesized under same conditions as Example 4 except1.01 g of 9-(ethylcarbonyl)-9′-methoxymethylfluorene is added in themother liquor addition stage, 0.38 g of9-(ethylcarbonyl)-9′-methoxymethylfluorene is added in the tolueneaddition stage.

Propylene polymerization is the same as in Example 1. Thecharacteristics of polymer products and processes are summarized inTable 8.

TABLE 8 Yield CE XS MFI Example g PP kg PP/g catalyst wt % dg/min 8 57057.0 4.8 6.7

Example 9

The catalyst is synthesized under same conditions as Example 8 except0.20 g of 9-(ethylcarbonyl)-9′-methoxymethylfluorene is added in the 1stactivation stage.

Propylene polymerization is the same as in Example 1. Thecharacteristics of polymer products and processes are summarized inTable 9.

TABLE 9 Yield CE XS MFI Example g PP kg PP/g catalyst wt % dg/min 9 51651.6 4.0 6.9

Example 10

The catalyst is synthesized under same conditions as Example 4 except0.96 g of 9-(methylcarbonyl)-9′-methoxymethylfluorene is added in themother liquor addition stage, 0.36 g of9-(methylcarbonyl)-9′-methoxymethylfluorene is added in the tolueneaddition stage.

Propylene polymerization is the same as in Example 1. Thecharacteristics of polymer products and processes are summarized inTable 10.

TABLE 10 Yield CE XS MFI Example g PP kg PP/g catalyst wt % dg/min 10292 29.2 6.5 6.8

What has been described above includes examples of the disclosedinformation. It is, of course, not possible to describe everyconceivable combination of components or methodologies for purposes ofdescribing the disclosed information, but one of ordinary skill in theart can recognize that many further combinations and permutations of thedisclosed information are possible. Accordingly, the disclosedinformation is intended to embrace all such alterations, modificationsand variations that fall within the spirit and scope of the appendedclaims. Furthermore, to the extent that the term “includes,” “has,”“involve,” or variants thereof is used in either the detaileddescription or the claims, such term is intended to be inclusive in amanner similar to the term “comprising” as “comprising” is interpretedwhen employed as a transitional word in a claim.

1. A solid titanium catalyst component for use in olefinicpolymerization, comprising: a titanium compound; a magnesium compound;and an internal electron donor compound comprising at least one ethergroup and at least one ketone group.
 2. The catalyst system of claim 1,wherein the internal electron donor compound comprises a compoundrepresented by Formula (II)

wherein R¹, R², R³, and R⁴ are identical or different and are eachindependently a substituted or unsubstituted hydrocarbon groupcomprising from 1 to about 30 carbon atoms.
 3. The catalyst system ofclaim 1, wherein the internal electron donor compound comprises acompound represented by Formula (II)

wherein R¹, R², R³, and R⁴ are identical or different and are eachindependently a linear or branched alkyl group comprising from 1 toabout 18 carbon atoms, a cycloaliphatic group comprising from about 3 toabout 18 carbon atoms, an aryl group comprising from about 6 to about 18carbon atoms, an alkylaryl group comprising from about 7 to about 18carbon atoms, or an arylalkyl group comprising from about 7 to about 18carbon atoms.
 4. The catalyst system of claim 1, wherein the internalelectron donor compound comprises a compound represented by Formula (II)

wherein R¹, R², R³, and R⁴ are identical or different and are eachindependently a substituted or unsubstituted hydrocarbon group, and R¹,C¹, and R² are a part of a substituted or unsubstituted cyclic orpolycyclic structure comprising from about 5 to about 14 carbon atoms.5. The catalyst system of claim 4, wherein the cyclic or polycyclicstructure comprises one or more substitutes selected from the groupconsisting of linear or branched alkyl groups comprising from 1 to about18 carbon atoms, cycloaliphatic groups comprising from about 3 to about18 carbon atoms, aryl groups comprising from about 6 to about 18 carbonatoms, alkylaryl groups comprising from about 7 to about 18 carbonatoms, and arylalkyl groups comprising from about 7 to about 18 carbonatoms.
 6. The catalyst system of claim 1, wherein the internal electrondonor compound comprises at least one selected from the group consistingof 9-(alkylcarbonyl)-9′-alkoxymethylfluorene including9-(methylcarbonyl)-9′-methoxymethylfluorene,9-(methylcarbonyl)-9′-ethoxymethylfluorene,9-(methylcarbonyl)-9′-propoxymethylfluorene,9-(methylcarbonyl)-9′-butoxymethylfluorene,9-(methylcarbonyl)-9′-pentoxymethylfluorene,9-(ethylcarbonyl)-9′-methoxymethylfluorene,9-(ethylcarbonyl)-9′-ethoxymethylfluorene,9-(ethylcarbonyl)-9′-propoxymethylfluorene,9-(ethylcarbonyl)-9′-butoxymethylfluorene,9-(ethylcarbonyl)-9′-pentoxymethylfluorene,9-(propylcarbonyl)-9′-methoxymethylfluorene,9-(propylcarbonyl)-9′-ethoxymethylfluorene,9-(propylcarbonyl)-9′-propoxymethylfluorene,9-(propylcarbonyl)-9′-butoxymethylfluorene,9-(propylcarbonyl)-9′-pentoxymethylfluorene,9-(butylcarbonyl)-9′-methoxymethylfluorene,9-(butylcarbonyl)-9′-ethoxymethylfluorene,9-(butylcarbonyl)-9′-propoxymethylfluorene,9-(butylcarbonyl)-9′-butoxymethylfluorene,9-(butylcarbonyl)-9′-pentoxymethylfluorene,9-(pentylcarbonyl)-9′-methoxymethylfluorene,9-(pentylcarbonyl)-9′-ethoxymethylfluorene,9-(pentylcarbonyl)-9′-propoxymethylfluorene,9-(pentylcarbonyl)-9′-butoxymethylfluorene,9-(pentylcarbonyl)-9′-pentoxymethylfluorene,9-(hexylcarbonyl)-9′-methoxymethylfluorene,9-(hexylcarbonyl)-9′-ethoxymethylfluorene,9-(hexylcarbonyl)-9′-propoxymethylfluorene,9-(hexylcarbonyl)-9′-butoxymethylfluorene,9-(hexylcarbonyl)-9′-pentoxymethylfluorene,9-(octylcarbonyl)-9′-methoxymethylfluorene,9-(octylcarbonyl)-9′-ethoxymethylfluorene,9-(octylcarbonyl)-9′-propoxymethylfluorene,9-(octylcarbonyl)-9′-butoxymethylfluorene,9-(octylcarbonyl)-9′-pentoxymethylfluorene,9-(i-octylcarbonyl)-9′-methoxymethylfluorene,9-(i-octylcarbonyl)-9′-ethoxymethylfluorene,9-(i-octylcarbonyl)-9′-propoxymethylfluorene,9-(i-octylcarbonyl)-9′-butoxymethylfluorene,9-(i-octylcarbonyl)-9′-pentoxymethylfluorene;9-(i-nonylcarbonyl)-9′-methoxymethylfluorene,9-(i-nonylcarbonyl)-9′-ethoxymethylfluorene,9-(i-nonylcarbonyl)-9′-propoxymethylfluorene,9-(i-nonylcarbonyl)-9′-butoxymethylfluorene,9-(i-nonylcarbonyl)-9′-pentoxymethylfluorene;9-(2-ethyl-hexylcarbonyl)-9′-methoxymethylfluorene,9-(2-ethyl-hexylcarbonyl)-9′-ethoxymethylfluorene,9-(2-ethyl-hexylcarbonyl)-9′-propoxymethylfluorene,9-(2-ethyl-hexylcarbonyl)-9′-butoxymethylfluorene,9-(2-ethyl-hexylcarbonyl)-9′-pentoxymethylfluorene,9-(phenylketone)-9′-methoxymethylfluorene,9-(phenylketone-9′-ethoxymethylfluorene,9-(phenylketone)-9′-propoxymethylfluorene,9-(phenylketone)-9′-butoxymethylfluorene,9-(phenylketone)-9′-pentoxymethylfluorene,9-(4-methylphenylketone)-9′-methoxymethylfluorene,9-(3-methylphenylketone)-9′-methoxymethylfluorene, and9-(2-methylphenylketone)-9′-methoxymethylfluorene.
 7. A catalyst systemfor use in olefinic polymerization, comprising: a solid titaniumcatalyst component comprising an internal electron donor compound, theinternal electron donor compound comprising at least one ether group andat least one ketone group; an organoaluminum compound; and anorganosilicon compound.
 8. The catalyst system of claim 7, wherein theinternal electron donor compound comprises a compound represented byFormula (II)

wherein R¹, R², R³, and R⁴ are identical or different and are eachindependently a substituted or unsubstituted hydrocarbon groupcomprising from 1 to about 30 carbon atoms.
 9. The catalyst system ofclaim 7, wherein the internal electron donor compound comprises acompound represented by Formula (II)

wherein R¹, R², R³, and R⁴ are identical or different and are eachindependently a linear or branched alkyl group comprising from 1 toabout 18 carbon atoms, a cycloaliphatic group comprising from about 3 toabout 18 carbon atoms, an aryl group comprising from about 6 to about 18carbon atoms, an alkylaryl group comprising from about 7 to about 18carbon atoms, or an arylalkyl group comprising from about 7 to about 18carbon atoms.
 10. The catalyst system of claim 7, wherein the internalelectron donor compound comprises a compound represented by Formula (II)

wherein R¹, R², R³, and R⁴ identical or different, and are eachindependently a substituted or unsubstituted hydrocarbon group, and R¹,C¹, and R² are a part of a substituted or unsubstituted cyclic orpolycyclic structure comprising from about 5 to about 14 carbon atoms.11. The catalyst system of claim 10, wherein the cyclic or polycyclicstructure comprises one or more substitutes selected from the groupconsisting of a linear or branched alkyl group comprising from 1 toabout 18 carbon atoms, a cycloaliphatic group comprising from about 3 toabout 18 carbon atoms, an aryl group comprising from about 6 to about 18carbon atoms, an alkylaryl group comprising from about 7 to about 18carbon atoms, and an arylalkyl group comprising from about 7 to about 18carbon atoms.
 12. The catalyst system of claim 7, wherein the internalelectron donor compound comprises at least one selected from the groupconsisting of 9-(alkylcarbonyl)-9′-alkoxymethylfluorene including9-(methylcarbonyl)-9′-methoxymethylfluorene,9-(methylcarbonyl)-9′-ethoxymethylfluorene,9-(methylcarbonyl)-9′-propoxymethylfluorene,9-(methylcarbonyl)-9′-butoxymethylfluorene,9-(methylcarbonyl)-9′-pentoxymethylfluorene,9-(ethylcarbonyl)-9′-methoxymethylfluorene,9-(ethylcarbonyl)-9′-ethoxymethylfluorene,9-(ethylcarbonyl)-9′-propoxymethylfluorene,9-(ethylcarbonyl)-9′-butoxymethylfluorene,9-(ethylcarbonyl)-9′-pentoxymethylfluorene,9-(propylcarbonyl)-9′-methoxymethylfluorene,9-(propylcarbonyl)-9′-ethoxymethylfluorene,9-(propylcarbonyl)-9′-propoxymethylfluorene,9-(propylcarbonyl)-9′-butoxymethylfluorene,9-(propylcarbonyl)-9′-pentoxymethylfluorene,9-(butylcarbonyl)-9′-methoxymethylfluorene,9-(butylcarbonyl)-9′-ethoxymethylfluorene,9-(butylcarbonyl)-9′-propoxymethylfluorene,9-(butylcarbonyl)-9′-butoxymethylfluorene,9-(butylcarbonyl)-9′-pentoxymethylfluorene,9-(pentylcarbonyl)-9′-methoxymethylfluorene,9-(pentylcarbonyl)-9′-ethoxymethylfluorene,9-(pentylcarbonyl)-9′-propoxymethylfluorene,9-(pentylcarbonyl)-9′-butoxymethylfluorene,9-(pentylcarbonyl)-9′-pentoxymethylfluorene,9-(hexylcarbonyl)-9′-methoxymethylfluorene,9-(hexylcarbonyl)-9′-ethoxymethylfluorene,9-(hexylcarbonyl)-9′-propoxymethylfluorene,9-(hexylcarbonyl)-9′-butoxymethylfluorene,9-(hexylcarbonyl)-9′-pentoxymethylfluorene,9-(octylcarbonyl)-9′-methoxymethylfluorene,9-(octylcarbonyl)-9′-ethoxymethylfluorene,9-(octylcarbonyl)-9′-propoxymethylfluorene,9-(octylcarbonyl)-9′-butoxymethylfluorene,9-(octylcarbonyl)-9′-pentoxymethylfluorene,9-(i-octylcarbonyl)-9′-methoxymethylfluorene,9-(i-octylcarbonyl)-9′-ethoxymethylfluorene,9-(i-octylcarbonyl)-9′-propoxymethylfluorene,9-(i-octylcarbonyl)-9′-butoxymethylfluorene,9-(i-octylcarbonyl)-9′-pentoxymethylfluorene;9-(i-nonylcarbonyl)-9′-methoxymethylfluorene,9-(i-nonylcarbonyl)-9′-ethoxymethylfluorene,9-(i-nonylcarbonyl)-9′-propoxymethylfluorene,9-(i-nonylcarbonyl)-9′-butoxymethylfluorene,9-(i-nonylcarbonyl)-9′-pentoxymethylfluorene;9-(2-ethyl-hexylcarbonyl)-9′-methoxymethylfluorene,9-(2-ethyl-hexylcarbonyl)-9′-ethoxymethylfluorene,9-(2-ethyl-hexylcarbonyl)-9′-propoxymethylfluorene,9-(2-ethyl-hexylcarbonyl)-9′-butoxymethylfluorene,9-(2-ethyl-hexylcarbonyl)-9′-pentoxymethylfluorene,9-(phenylketone)-9′-methoxymethylfluorene,9-(phenylketone-9′-ethoxymethylfluorene,9-(phenylketone)-9′-propoxymethylfluorene,9-(phenylketone)-9′-butoxymethylfluorene,9-(phenylketone)-9′-pentoxymethylfluorene,9-(4-methylphenylketone)-9′-methoxymethylfluorene,9-(3-methylphenylketone)-9′-methoxymethylfluorene, and9-(2-methylphenylketone)-9′-methoxymethylfluorene.
 13. A method ofmaking a solid titanium catalyst component for a catalyst system used inolefinic polymerization, comprising: contacting a magnesium compound anda titanium compound with an internal electron donor compound comprisingat least one ether group and at least one ketone group.
 14. The methodof claim 13, wherein the internal electron donor compound comprises acompound represented by Formula (II)

wherein R¹, R², R³, and R⁴ are identical or different and are eachindependently a substituted or unsubstituted hydrocarbon groupcomprising from 1 to about 30 carbon atoms.
 15. The method of claim 13,wherein the internal electron donor compound comprises a compoundrepresented by Formula (II)

wherein R¹, R², R³, and R⁴ are identical or different and are eachindependently a linear or branched alkyl group comprising from 1 toabout 18 carbon atoms, a cycloaliphatic group comprising from about 3 toabout 18 carbon atoms, an aryl group comprising from about 6 to about 18carbon atoms, an alkylaryl group comprising from about 7 to about 18carbon atoms, or an arylalkyl group comprising from about 7 to about 18carbon atoms.
 16. The catalyst system of claim 13, wherein the internalelectron donor compound comprises a compound represented by Formula (II)

wherein R¹, R², R³ and R⁴ identical or different, and are eachindependently a substituted or unsubstituted hydrocarbon group, and R¹,C¹, and R² are a part of a substituted or unsubstituted cyclic orpolycyclic structure comprising from about 5 to about 14 carbon atoms.17. A method of polymerizing or copolymerizing an olefin, comprising:contacting an olefin with a catalyst system comprising a solid titaniumcatalyst component comprising an internal electron donor compound, theinternal electron donor compound comprising at least one ether group andat least one ketone group; an organoaluminum compound having at leastone aluminum-carbon bond; and an organosilicon compound.
 18. The methodof claim 17, wherein the internal electron donor compound comprises acompound represented by Formula (II)

wherein R¹, R², R³, and R⁴ are identical or different and are eachindependently a substituted or unsubstituted hydrocarbon groupcomprising from 1 to about 30 carbon atoms.
 19. The method of claim 17,wherein the internal electron donor compound comprises a compoundrepresented by Formula (II)

wherein R¹, R², R³, and R⁴ are identical or different and are eachindependently a linear or branched alkyl group comprising from 1 toabout 18 carbon atoms, a cycloaliphatic group comprising from about 3 toabout 18 carbon atoms, an aryl group comprising from about 6 to about 18carbon atoms, an alkylaryl group comprising from about 7 to about 18carbon atoms, or an arylalkyl group comprising from about 7 to about 18carbon atoms.
 20. The method of claim 17, wherein the internal electrondonor compound comprises a compound represented by Formula (II)

wherein R¹, R², R³, and R⁴ identical or different, and are eachindependently a substituted or unsubstituted hydrocarbon group, and R¹,C¹, and R² are a part of a substituted or unsubstituted cyclic orpolycyclic structure comprising from about 5 to about 14 carbon atoms.